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Method for electrochemical synthesis of tetraarylhydrazine compound

A compound and aryl hydrazine technology, applied in the field of electrochemical organic synthesis, can solve the problems of expensive catalyst, unfriendly environment, and small application range of substrates, and achieve a simple and efficient reaction system, easy availability of raw materials, and wide application scope of substrates. Effect

Active Publication Date: 2020-06-05
QILU UNIV OF TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] In view of the deficiencies in the prior art, especially in the existing synthetic methods of tetraarylhydrazine compounds, there are shortcomings such as the need for additional chemical oxidants or the catalysis of transition metals, the scope of substrate application is small, the catalyst is expensive, and the environment is not friendly. The present invention provides A method for synthesizing tetraarylhydrazine compounds with simple and easy-to-obtain raw materials, simple reaction operation, wide substrate applicability, high atom utilization rate, green and efficient

Method used

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  • Method for electrochemical synthesis of tetraarylhydrazine compound
  • Method for electrochemical synthesis of tetraarylhydrazine compound
  • Method for electrochemical synthesis of tetraarylhydrazine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0060] Add 0.25mmol of N-(4-chlorophenyl)-5-fluoropyridin-2-amine, 0.5mmol of tetrabutylammonium iodide as an electrolyte, 7.0mL of acetonitrile, and 0.5mL of methanol in a three-necked flask And a magnetic stirrer, nitrogen as a protective gas, a platinum sheet (1.0cm×1.0cm) as an anode and a cathode, turn on the power, adjust the current to 5.0mA, and react at 60°C for 10 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography. The eluent was a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 10:1 to obtain a tetraarylhydrazine compound with a yield of 99%. 2a.

[0061]

[0062] The product 2a that present embodiment obtains 1 H-NMR spectrum such as figure 2 as shown, 13 C-NMR spectrum such as image 3 As shown, the NMR data are as follows:

[0063] 1 H-NMR (400MHz, CDCl 3 ): δ8.11(d, J=2.6Hz, 2H), 7.39(d, J=8.7Hz, 4H), 7.30-7.24(m, 2H), 7.22(d, J=8...

Embodiment 2

[0067] Into a three-necked flask were sequentially added 0.25 mmol of 5-fluoro-N-(p-tolyl)pyridin-2-amine, 0.5 mmol of tetrabutylammonium iodide as an electrolyte, 7.0 mL of acetonitrile, 0.5 mL of methanol, and a magnetic Stirrer, nitrogen as protective gas, platinum sheet (1.0cm×1.0cm) as anode and cathode, power on, adjust current to 5.0mA, react at 60°C for 10 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography. The eluent was a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 10:1 to obtain 92% tetraarylhydrazine compound 2b, structural formula as follows:

[0068]

[0069] Product 2b 1 H-NMR spectrum such as Figure 4 as shown, 13 C-NMR spectrum such as Figure 5 As shown, the NMR data are as follows:

[0070] 1 H-NMR (400MHz, CDCl 3 ):δ8.09(d,J=2.8Hz,2H),7.35(d,J=8.4Hz,4H),7.25-7.19(m,2H),7.07(d,J=8.3Hz,4H),6.95 (dd,J=9.1,3.4Hz,2H),2.27(s,6...

Embodiment 3

[0074] 0.25mmol of N-(4-(tert-butyl)phenyl)-5-fluoropyridin-2-amine, 0.5mmol of tetrabutylammonium iodide as electrolyte, 7.0mL of acetonitrile, 0.5mL of methanol and a magnetic stirrer, nitrogen as a protective gas, platinum sheets (1.0cm×1.0cm) as anode and cathode, turn on the power, adjust the current to 5.0mA, and react at 60°C for 10 hours. After the reaction was completed, the solvent was removed by rotary evaporation, and the crude product was purified by column chromatography. The eluent was a mixed solvent of petroleum ether and ethyl acetate with a volume ratio of 10:1 to obtain a tetraarylhydrazine compound with a yield of 95%. 2c, the structural formula is as follows:

[0075]

[0076] Product 2c 1 H-NMR spectrum such as Image 6 as shown, 13 C-NMR spectrum such as Figure 7 As shown, the NMR data are as follows:

[0077] 1 H-NMR (400MHz, CDCl 3 ): δ8.11(d, J=2.6Hz, 2H), 7.42(d, J=8.6Hz, 4H), 7.28(d, J=8.7Hz, 4H), 7.24-7.18(m, 2H), 6.96 (dd,J=9.1,3.3Hz,...

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Abstract

The invention relates to a method for electrochemical synthesis of a tetraarylhydrazine compound, and belongs to the technical field of electrochemical organic synthesis. The method comprises the following steps: sequentially adding a diarylamine compound, a solvent and an electrolyte into an unseparated electrolytic tank, inserting an anode and a cathode, stirring, electrifying, reacting under the conditions of constant current and nitrogen, and after the reaction is finished, separating and purifying to obtain the product tetraarylhydrazine compound. According to the method, tetrabutylammonium iodide is used as an electrolyte for a reaction, and a metal catalyst, an oxidizing agent or acid-base does not need to be additionally added, so that toxic substances are effectively prevented from being used, the reaction is performed under non-toxic and harmless conditions, and a reaction system is simple, efficient and environment-friendly.

Description

technical field [0001] The invention discloses a method for electrochemically synthesizing tetraarylhydrazine compounds, belonging to the technical field of electrochemical organic synthesis. Background technique [0002] Arylhydrazine compounds are a common organic framework: tetraarylhydrazine is a unique framework structure in natural products dixiamycin A and dixiamycin B. [0003] [0004] Besides, tetraarylhydrazines can also be used as electrocatalysts. The main methods for synthesizing tetraarylhydrazines in existing reports are: (1) In 2019, Yu Wenquan et al. used the conventional catalytic oxidative coupling of secondary amines and chemical oxidants (iodine simple substances) (Org.Biomol.Chem. , 2019, 17, 3446-3450.); (2) 2017 et al described the oxidative C-C and N-N coupling reactions of diarylamines in the presence of various iron catalysts (Angew.Chem.Int.Ed., 2017, 56, 549-553); (3) recently, Stahl and his Colleagues developed an aerobic oxidative dimer...

Claims

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Application Information

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IPC IPC(8): C25B3/02C25B3/23
CPCC25B3/23
Inventor 陈建宾吕士德
Owner QILU UNIV OF TECH
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